EP0323625A2 - Process for preparing 3-[2-chloro-2(4-chlorophenyl)-vinyl]-2,2-dimethyl-cyclopropane carboxylic acid - Google Patents

Process for preparing 3-[2-chloro-2(4-chlorophenyl)-vinyl]-2,2-dimethyl-cyclopropane carboxylic acid Download PDF

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EP0323625A2
EP0323625A2 EP88121699A EP88121699A EP0323625A2 EP 0323625 A2 EP0323625 A2 EP 0323625A2 EP 88121699 A EP88121699 A EP 88121699A EP 88121699 A EP88121699 A EP 88121699A EP 0323625 A2 EP0323625 A2 EP 0323625A2
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chlorophenyl
chloro
dimethyl
hexen
vinyl
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EP0323625A3 (en
EP0323625B1 (en
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Reinhard Dr. Lantzsch
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides

Definitions

  • the present invention relates to a new process for the preparation of 3- (2-chloro-2- (4-chlorophenyl) vinyl) -2,2-dimethylcyclopropanecarboxylic acid.
  • This carboxylic acid is known by reacting 3-chloro-3- (4-chlorophenyl) propenal with methyl isopropyl ketone, bromination of the resulting 4,4-dimethyl-1,3-dichloro-1- (4-chlorophenyl) - 1-Hexen-5-one with bromine and subsequent cyclization with ring narrowing in the presence of aqueous alkalis (EP-OS 95 047).
  • EP-OS 95 047 aqueous alkalis
  • the resulting carboxylic acids or carboxylic acid esters can be converted into their derivatives, e.g. Transfer salts, esters, amides, halides.
  • the overall yield of the desired carboxylic acid is increased from 41.1 or 44.7 to 67.5%. It was particularly surprising that the desired products could be obtained in such high yields in the reactions according to the invention.
  • the starting products used to carry out the reactions according to the invention are known.
  • the first step of the reaction according to the invention can be carried out with or without a diluent.
  • the starting products are used in an approximately equimolar ratio.
  • Possible diluents are: hydrocarbons such as cyclohexane, petroleum ether, benzene, toluene, chlorinated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride or chlorenzenes, ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, alipane such as acetic acid, propionic acid.
  • hydrocarbons such as cyclohexane, petroleum ether, benzene, toluene
  • chlorinated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride or chlorenzenes
  • ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, tetrahydrofuran, dioxane
  • the reaction is carried out in the presence of at least equimolar amounts of hydrogen chloride. An up to 4 molar excess can be advantageous.
  • the reaction is carried out at temperatures between -20 ° C and + 30 ° C, preferably between 0 ° C and + 20 ° C.
  • It can be operated at normal pressure or increased pressure.
  • the 4,4-dimethyl-1,3,6-trichloro-1- (4-chlorophenyl) -1-hexen-5-one obtained in the first stage is diluted with an aqueous base or with alcoholates implemented.
  • Possible diluents are: alcohols such as methanol, ethanol, t-butanol.
  • Possible bases are: aqueous alkali such as sodium hydroxide solution, potassium hydroxide solution.
  • Possible alcoholates are: sodium or potassium alcoholates such as ethylates, methylates.
  • the base is advantageously used in an excess of 2 to 10 equivalents per equivalent of 4,4-dimethyl-1,3,6-trichloro-1- (4-chlorophenyl) -1-hexen-5-one.
  • the reaction temperature can be varied over a wide range. It is usually carried out at room temperature.
  • reaction mixture is worked up in a customary manner by neutralization, distilling off the solvent in vacuo, extraction of the ester formed or liberation of the acid formed by acidification with mineral acids and subsequent extraction.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract

A novel two-step process for preparing 3-(2-chloro- 2-(4-chlorophenyl)vinyl)-2,2-dimethylcyclopropanecarboxylic acid, starting from 3-chloro-3-(4-chlorophenyl)propenal and chloromethyl isopropyl ketone.

Description

Die vorliegende Erfindung betrifft ein neues Verfahren zur Herstellung von 3-(2-Chlor-2-(4-chlorphenyl)-vinyl)-­2,2-dimethylcyclopropancarbonsäure.The present invention relates to a new process for the preparation of 3- (2-chloro-2- (4-chlorophenyl) vinyl) -2,2-dimethylcyclopropanecarboxylic acid.

Es ist bekannt diese Carbonsäure durch Umsetzung von 3-­Chlor-3-(4-chlorphenyl)-propenal mit Methyl-isopropyl­keton, Bromierung des dabei entstehenden 4,4-Dimethyl-­1,3-dichlor-1-(4-chlorphenyl)-1-hexen-5-on mit Brom und anschließende Cyclisierung unter Ringverengung in Gegen­wart wäßriger Laugen herzustellen (EP-OS 95 047). Die Wirtschaftlichkeit dieser Reaktionsfolge ist jedoch nicht voll befriedigend.This carboxylic acid is known by reacting 3-chloro-3- (4-chlorophenyl) propenal with methyl isopropyl ketone, bromination of the resulting 4,4-dimethyl-1,3-dichloro-1- (4-chlorophenyl) - 1-Hexen-5-one with bromine and subsequent cyclization with ring narrowing in the presence of aqueous alkalis (EP-OS 95 047). However, the economy of this reaction sequence is not entirely satisfactory.

Es wurde nun gefunden, daß man 3-(2-Chlor-2-(4-chlorphe­nyl)-vinyl)-2,2-dimethylcyclopropancarbonsäure und ihre Derivate erhält, indem man in einer ersten Stufe 3-­Chlor-3-(4-chlorphenyl)-propenal mit Chlormethyliso­propylketon umsetzt und das entstandene 4,4-Dimethyl-­ 1,3,6-trichlor-1-(4-chlorphenyl)-1-hexen-5-on gegebe­nenfalls ohne Isolierung in Gegenwart wäßriger Basen oder in Gegenwart von Alkoholaten umsetzt.It has now been found that 3- (2-chloro-2- (4-chlorophenyl) vinyl) -2,2-dimethylcyclopropanecarboxylic acid and its derivatives are obtained by, in a first step, 3-chloro-3- (4- chlorphenyl) propenal with chloromethyl isopropyl ketone and the resulting 4,4-dimethyl 1,3,6-trichloro-1- (4-chlorophenyl) -1-hexen-5-one, optionally without isolation, in the presence of aqueous bases or in the presence of alcoholates.

Die entstehenden Carbonsäuren bzw. Carbonsäureester lassen sich nach allgemein bekannten Methoden in ihre Derivate wir z.B. Salze, Ester, Amide, Halogenide überführen.The resulting carboxylic acids or carboxylic acid esters can be converted into their derivatives, e.g. Transfer salts, esters, amides, halides.

Durch diese Art der Reaktionsführung läßt sich die Carbonsäure in wesentlich besseren Ausbeuten erhalten als nach den bekannten Methoden. Um einen aussagekräfti­gen Vergleich der Ausbeuten anstellen zu können müssen folgende Verfahren zusammengefaßt und verglichen werden:

  • I bekannt
    a) 3-Chlor-3-(4-chlorphenyl)-propenal umgesetzt mit Methylisopropylketon, Ausbeute gemäß EP-OS 95 047 Beispiel 1 = 72,7 %
    b) 4,4-Dimethyl-1,3-dichlor-(4-chlorphenyl)-1-hexen-5-­on umgesetzt mit Brom, Ausbeute gemäß EP-OS 95 047 Beispiel 2 (Nacharbeitung) = 75 %
    c) 4,4-Dimethyl-1,3-dichlor-6-brom-(4-chlorphenyl)-1-­hexen-5-on umgesetzt mit wäßrigem Alkali, Ausbeute gemäß EP-OS 95 047 Beispiel 3 (Nacharbeitung) = 82 %
    Gesamtausbeute der Reaktionen a + b + c = 44,7 %.
  • II Vergleich
    a) 3-Chlor-3-(4-chlorphenyl)-propenal umgesetzt mit Methylisopropylketon, Ausbeute gemäß EP-OS 95 047 Beispiel 1 = 72,7 %
    b) 4,4-Dimethyl-1,3-dichlor-(4-chlorphenyl)-1-hexen-5-­on umgesetzt mit Chlor, Ausbeute = 60,2 % (dieses Beispiel ist im Stand der Technik nicht beschrie­ben)
    c) 4,4-Dimethyl-1,3,6-trichlor-1-(4-chlorphenyl)-1-­hexen-5-on umgesetzt mit wäßrigem Alkali, Ausbeute = 94 % (dieses Beispiel ist im Stand der Technik nicht beschrieben)
    Gesamtausbeute der Reaktionen a + b + c = 41,1 %.
  • II erfindungsgemäß
    a) Methylisopropylketon umgesetzt mit Chlor, Ausbeute = 78 %
    b) 3-Chlor-3-(4-chorphenyl)-propenal umgesetzt mit Chlormethylisopropylketon, Ausbeute = 92 %
    c) 4,4-Dimethyl-1,3,6-trichlor-1-(4-chlorphenyl)-1-­hexen-5-on umgesetzt mit mit wäßrigem Alkali, Ausbeute = 94 %
    Gesamtausbeute der Reaktionen a + b + c = 67,5 %.
This type of reaction allows the carboxylic acid to be obtained in significantly better yields than by the known methods. In order to be able to make a meaningful comparison of the yields, the following processes must be summarized and compared:
  • I known
    a) 3-chloro-3- (4-chlorophenyl) propenal reacted with methyl isopropyl ketone, yield according to EP-OS 95 047 Example 1 = 72.7%
    b) 4,4-dimethyl-1,3-dichloro- (4-chlorophenyl) -1-hexen-5-one reacted with bromine, yield according to EP-OS 95 047 Example 2 (reworking) = 75%
    c) 4,4-Dimethyl-1,3-dichloro-6-bromo- (4-chlorophenyl) -1-hexen-5-one reacted with aqueous alkali, yield according to EP-OS 95 047 Example 3 (reworking) = 82 %
    Overall yield of reactions a + b + c = 44.7%.
  • II comparison
    a) 3-chloro-3- (4-chlorophenyl) propenal reacted with methyl isopropyl ketone, yield according to EP-OS 95 047 Example 1 = 72.7%
    b) 4,4-dimethyl-1,3-dichloro (4-chlorophenyl) -1-hexen-5-one reacted with chlorine, yield = 60.2% (this example is not described in the prior art)
    c) 4,4-Dimethyl-1,3,6-trichloro-1- (4-chlorophenyl) -1-hexen-5-one reacted with aqueous alkali, yield = 94% (this example is not described in the prior art )
    Overall yield of reactions a + b + c = 41.1%.
  • II according to the invention
    a) Methyl isopropyl ketone reacted with chlorine, yield = 78%
    b) 3-chloro-3- (4-chorphenyl) propenal reacted with chloromethylisopropyl ketone, yield = 92%
    c) 4,4-dimethyl-1,3,6-trichloro-1- (4-chlorophenyl) -1-hexen-5-one reacted with with aqueous alkali, yield = 94%
    Overall yield of reactions a + b + c = 67.5%.

Durch die erfindungsgemäße Reaktionsführung wird eine Steigerung der Gesamtausbeute der gewünschten Carbon­säure von 41,1 bzw. 44,7 auf 67,5 % erreicht. Besonders überraschend war, daß in den erfindungsgemäßen Reaktio­nen die gewünschten Produkte in so hohen Ausbeuten erhalten werden konnten.By carrying out the reaction according to the invention, the overall yield of the desired carboxylic acid is increased from 41.1 or 44.7 to 67.5%. It was particularly surprising that the desired products could be obtained in such high yields in the reactions according to the invention.

Die zur Durchführung der erfindungsgemäßen Reaktionen eingesetzten Ausgangsprodukte sind bekannt. Die erste Stufe der erfindungsgemäßen Reaktion kann mit oder ohne Verdünnungsmittel durchgeführt werden. Die Ausgangspro­dukte werden in etwa äquimolarem Verhältnis eingesetzt. Ein Überschuß von bis zu 4 Äquivalenten Chlormethyliso­propylketon, bezogen auf das 3-Chlor-3-(4-chlorphenyl)-­propenal ist besonders beim Arbeiten ohne Verdünnungs­mittel vorteilhaft.The starting products used to carry out the reactions according to the invention are known. The first step of the reaction according to the invention can be carried out with or without a diluent. The starting products are used in an approximately equimolar ratio. An excess of up to 4 equivalents of chloromethyl isopropyl ketone, based on the 3-chloro-3- (4-chlorophenyl) propenal, is particularly advantageous when working without a diluent.

Als Verdünnungsmittel komen in Frage: Kohlenwasserstoffe wie Cyclohexan, Petrolether, Benzol, Toluol, Chlorkoh­lenwasserstoffe wie Dichlormethan, Chloroform, Tetra­chlorkohlenstoff oder Chlorenzole, Ether wie Diethyl­ether, Diisopropylether, Methyl-t-butylether, Tetrahy­drofuran, Dioxan, 1,2-Dimethoxyethan, aliphatische Säuren wie Essigsäure, Propionsäure.Possible diluents are: hydrocarbons such as cyclohexane, petroleum ether, benzene, toluene, chlorinated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride or chlorenzenes, ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, alipane such as acetic acid, propionic acid.

Die Reaktion wird in Gegenwart mindestens äquimolarer Mengen Chlorwasserstoff durchgeführt. Ein bis zu 4 molarer Überschuß kann von Vorteil sein.The reaction is carried out in the presence of at least equimolar amounts of hydrogen chloride. An up to 4 molar excess can be advantageous.

Die Reaktion wird bei Temperaturen zwischen -20°C und +30°C, vorzugsweise zwischen 0°C und +20°C durchge­führt.The reaction is carried out at temperatures between -20 ° C and + 30 ° C, preferably between 0 ° C and + 20 ° C.

Es kann bei Normaldruck oder erhöhtem Druck gearbeitet werden.It can be operated at normal pressure or increased pressure.

Zur Aufarbeitung wird Lösungsgmittel, überschüssiges Chlormethylisopropylketon sowie Chlorwasserstoff abde­stilliert. Das so erhaltene Produkt kann ohne weitere Reinigung in die nächste Stufe eingesetzt werden.For working up, solvent, excess chloromethyl isopropyl ketone and hydrogen chloride are distilled off. The product obtained in this way can be used in the next step without further purification.

In der zweiten Stufe wird das in der ersten Stufe erhal­tene 4,4-Dimethyl-1,3,6-trichlor-1-(4-chlorphenyl)-1-­hexen-5-on in einem Verdünnungsmittel mit einer wäßrigen Base oder mit Alkoholaten umgesetzt.In the second stage, the 4,4-dimethyl-1,3,6-trichloro-1- (4-chlorophenyl) -1-hexen-5-one obtained in the first stage is diluted with an aqueous base or with alcoholates implemented.

Als Verdünnungsmittel kommen in Frage: Alkohole wie Methanol, Ethanol, t-Butanol. Als Basen kommen in Frage: wäßriges Alkali wie Natronlauge, Kalilauge. Als Alkoho­late kommen in Frage: Natrium- oder Kaliumalkoholate wie Ethylate, Methylate.Possible diluents are: alcohols such as methanol, ethanol, t-butanol. Possible bases are: aqueous alkali such as sodium hydroxide solution, potassium hydroxide solution. Possible alcoholates are: sodium or potassium alcoholates such as ethylates, methylates.

Die Base wird vorteilhafterweise in einem Überschuß von 2 bis 10 Äquivalenten pro Äquivalent 4,4-Dimethyl-1,3,6-­trichlor-1-(4-chlorphenyl)-1-hexen-5-on eingesetzt. Die Reaktionstemperatur kann in größeren Bereichen variiert werden. Üblicherweise wird bei Raumtemperatur gearbei­tet.The base is advantageously used in an excess of 2 to 10 equivalents per equivalent of 4,4-dimethyl-1,3,6-trichloro-1- (4-chlorophenyl) -1-hexen-5-one. The reaction temperature can be varied over a wide range. It is usually carried out at room temperature.

Die Aufarbeitung des Reaktionsgemisches erfolgt in üblicher Weise durch Neutralisation, Abdestillieren des Lösungsmittels in Vakuum, Extraktion des entstandenen Esters oder Freisetzen der entstandenen Säure durch Ansäuern mit Mineralsäuren und anschließende Extraktion.The reaction mixture is worked up in a customary manner by neutralization, distilling off the solvent in vacuo, extraction of the ester formed or liberation of the acid formed by acidification with mineral acids and subsequent extraction.

Beispiel 1 (erste Stufe der erfindungsgemäßen Reaktion) Example 1 (first stage of the reaction according to the invention)

Figure imgb0001
Figure imgb0001

20,1 g (0,1 Mol) Z-3-Chlor-(4-chlorphenyl)-propenal und 36,2 g 1-Chlor-3-methyl-2-butanon (93 %ig = 0,28 Mol) werden vorgelegt und unter Rühren bei 10 bis 15°C 5 Minuten Chlorwasserstoff eingeleitet. Man rührt 12 Stunden bei 20°C nach.20.1 g (0.1 mol) of Z-3-chloro (4-chlorophenyl) propenal and 36.2 g of 1-chloro-3-methyl-2-butanone (93% = 0.28 mol) submitted and initiated with stirring at 10 to 15 ° C for 5 minutes hydrogen chloride. The mixture is stirred at 20 ° C for 12 hours.

Anschließend destilliert man bei 100°C Badtemperatur/­80 mbar das überschüssige Chlormethylbutanon ab.The excess chloromethylbutanone is then distilled off at a bath temperature of 100 ° C./80 mbar.

Der Rückstand wird bei 60°C/O,1 mbar von niedrig siedenden Nebenkomponenten befreit und kann direkt weiter umgesetzt werden: 36,4 g; Gehalt: 86 % = 92 % der Theorie. Durch Zugabe von wenig Methanol erhält man 25,8 g gelbe Kristalle vom Schmelzpunkt 72 bis 74°C.The residue is freed from low-boiling secondary components at 60 ° C./0.1 mbar and can be directly reacted further: 36.4 g; Content: 86% = 92% of theory. By adding a little methanol, 25.8 g of yellow crystals of melting point 72 to 74 ° C. are obtained.

Beispiel 2(zweite Stufe der erfindungsgemäßen Reaktion Example 2 (second stage of the reaction according to the invention

Zu einer Suspension von 7 g (0,02 Mol) 4,4-Dimethyl-1,3-­dichlor-6-chlor-1-(4-chlorphenyl)-1-hexen-5-on in 20 ml Methanol werden bei 20 bis 25°C innerhalb 30 Minuten 10 g (0,11 Mol) 45 %ige Natronlauge zugetropft. An­schließend wird 3 Stunden bei 35 bis 40°C nachgerührt. Nach der Neutralisation mit konzentrierter Salzsäure wird die Hauptmenge an Methanol im Vakuum abgedampft. Die zurückbleibende Lösung wird mit konzentrierter Salzsäure auf pH 3 gestellt mit Toluol bei 40°C extra­hiert und das Lösungsmittel abgezogen. Man erhält 5,36 g (94 % der Theorie) cis/trans-3-(Z-2-Chlor-2-(4-chlor­phenyl)-vinyl-2,2-dimethyl-cyclopropancarbonsäure.A suspension of 7 g (0.02 mol) of 4,4-dimethyl-1,3-dichloro-6-chloro-1- (4-chlorophenyl) -1-hexen-5-one in 20 ml of methanol is added at 20 10 g (0.11 mol) of 45% sodium hydroxide solution were added dropwise to 25 ° C. in the course of 30 minutes. The mixture is then stirred at 35 to 40 ° C for 3 hours. After neutralization with concentrated hydrochloric acid, the main amount of methanol is evaporated off in vacuo. The remaining solution is adjusted to pH 3 with concentrated hydrochloric acid, extracted with toluene at 40 ° C. and the solvent is stripped off. 5.36 g (94% of theory) of cis / trans-3- (Z-2-chloro-2- (4-chlorophenyl) vinyl-2,2-dimethyl-cyclopropanecarboxylic acid are obtained.

Beispiel a (Herstellung des Ausgangsprodukts) Example a (preparation of the starting product)

Figure imgb0002
CO-CH₂Cl
Figure imgb0002
CO-CH₂Cl

86 g (1 Mol) Methylisopropylketon und 200 ml Methanol werden vorgelegt. Dann wird unter Kühlung (stark exo­therm) Chlorwasserstoff eingeleitet (ca. 4 g).86 g (1 mol) of methyl isopropyl ketone and 200 ml of methanol are introduced. Then hydrogen chloride is introduced (about 4 g) with cooling (strongly exothermic).

Anschließend leitet man bei -5°C bis -10°C 71 g (1 Mol) Chlor ein. Nach zehnminütiger Nachrührzeit wird das Gemisch aus Methanol und Chlorwasserstoff bei 25°C/40 mbar abdestilliert (es kann für den nächsten Ansatz verwendet werden.Then 71 g (1 mol) of chlorine are passed in at -5 ° C. to -10 ° C. After stirring for ten minutes, the mixture of methanol and hydrogen chloride is distilled off at 25 ° C./40 mbar (it can be used for the next batch.

Der Rückstand wiegt 169,5 g und wird im Vakuum über eine 30 cm-Kolonne fraktioniert. Man erhält 94 g 1-Chlor-3-­methyl-2-butanon vom Siedepunkt 73 bis 75°C/64 mbar. Dies entspricht einer Ausbeute von 78 % Theorie.The residue weighs 169.5 g and is fractionated in vacuo over a 30 cm column. 94 g of 1-chloro-3-methyl-2-butanone with a boiling point of 73 to 75 ° C./64 mbar are obtained. This corresponds to a yield of 78% theory.

Beispiel b) (Vergleich) Example b) (comparison)

Figure imgb0003
15,3 g (0,05 Mol) 4,4-Dimethyl-1,3-dichlor-1-(4-chlor­phenyl)-hexen-5-on werden in 50 ml Essigsäure, die etwas Chlorwasserstoff enthält, gelöst. Unter gutem Rühren werden 3,6 g Chlor (0,05 Mol) bei 15°C eingeleitet. Man rührt eine Stunde bei ca. 15°C nach und engt am Dampf­strahler ein.
Figure imgb0003
 15.3 g (0.05 mol) of 4,4-dimethyl-1,3-dichloro-1- (4-chlorophenyl) -hexen-5-one are dissolved in 50 ml of acetic acid, which contains some hydrogen chloride. 3.6 g of chlorine (0.05 mol) are introduced at 15 ° C. with thorough stirring. The mixture is stirred for an hour at about 15 ° C and concentrated on a steam jet.

Man erhält 13,2 g eines Produktgemisches, das zu 77,5 % aus 4,4-Dimethyl-1,3,6-trichlor-1-(4-chlor-phenyl)-1-­hexen-5-on besteht.
Dies entspricht einer Ausbeute von 60,2 % der Theorie.13.2 g of a product mixture are obtained, 77.5% of which consists of 4,4-dimethyl-1,3,6-trichloro-1- (4-chlorophenyl) -1-hexen-5-one.
This corresponds to a yield of 60.2% of theory.

Claims (1)

Verfahren zur Herstellung von 3-(2-Chlor-2-(4-chlor­phenyl)-vinyl)-2,2-dimethylcyclopropancarbonsäure, -estern und ihren Derivaten, dadurch gekennzeichnet, daß man in einer ersten Stufe 3-Chlor-3-(4-chlorphenyl)-­propenal mit Chlormethyl-isopropylketon umsetzt und in einer zweiten Stufe das entstandene 4,4-Dimethyl-1,3,6-­trichlor-1-(4-chlorphenyl)-1-hexen-5-on gegebenenfalls ohne Isolierung in Gegenwart wäßriger Basen oder in Gegenwart von Alkoholaten umsetzt und gegebenenfalls anschließend die entstandene Säure oder ihre Ester in üblicher Weise derivatisiert.Process for the preparation of 3- (2-chloro-2- (4-chlorophenyl) vinyl) -2,2-dimethylcyclopropanecarboxylic acid, esters and their derivatives, characterized in that in a first step 3-chloro-3- ( 4-chlorophenyl) propenal is reacted with chloromethyl isopropyl ketone and, in a second stage, the 4,4-dimethyl-1,3,6-trichloro-1- (4-chlorophenyl) -1-hexen-5-one formed, optionally without isolation in the presence of aqueous bases or in the presence of alcoholates and, if appropriate, subsequently derivatizing the resulting acid or its esters in a conventional manner.
EP88121699A 1988-01-05 1988-12-27 Process for preparing 3-[2-chloro-2(4-chlorophenyl)-vinyl]-2,2-dimethyl-cyclopropane carboxylic acid Expired - Lifetime EP0323625B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3800097A DE3800097A1 (en) 1988-01-05 1988-01-05 METHOD FOR PRODUCING 3- (2-CHLORINE-2- (4-CHLORINE-PHENYL) -VINYL) - 2,2-DIMETHYLCYCLOPROPANCARBONIC ACID
DE3800097 1988-01-05

Publications (3)

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EP0323625A2 true EP0323625A2 (en) 1989-07-12
EP0323625A3 EP0323625A3 (en) 1990-07-25
EP0323625B1 EP0323625B1 (en) 1992-09-09

Family

ID=6344830

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88121699A Expired - Lifetime EP0323625B1 (en) 1988-01-05 1988-12-27 Process for preparing 3-[2-chloro-2(4-chlorophenyl)-vinyl]-2,2-dimethyl-cyclopropane carboxylic acid

Country Status (6)

Country Link
US (1) US4897505A (en)
EP (1) EP0323625B1 (en)
JP (1) JP2720934B2 (en)
AU (1) AU607030B2 (en)
DE (2) DE3800097A1 (en)
ZA (1) ZA8942B (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0095696A1 (en) * 1982-06-02 1983-12-07 Bayer Ag Process for the preparation of 2,2-dimethyl-3-aryl-cyclopropane carboxylic acids and their esters, intermediate products therefor and processes for their preparation

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4183942A (en) * 1976-08-27 1980-01-15 Fmc Corporation Insecticidal (β-phenyl-β-substituted-vinyl)cyclopropanecarboxylates
US4160842A (en) * 1976-08-27 1979-07-10 Fmc Corporation Insecticidal [β-(substituted-phenyl)vinyl]cyclopropanecarboxylates
US4157397A (en) * 1976-08-27 1979-06-05 Fmc Corporation Insecticidal (β-phenylvinyl)cyclopropanecarboxylates
ZA775160B (en) * 1976-08-27 1978-07-26 Fmc Corp Insecticidal styryl- and substituted-styrylcyclopropanecarboxylates
DE2916401A1 (en) * 1979-04-23 1980-11-06 Bayer Ag PROCESS FOR THE PREPARATION OF 3-(2-ARYLVINYL)-2,2-DIMETHYL-CYCLOPROPAN-1-CARBON ACID ESTERS AND NOVEL INTERMEDIATE PRODUCTS THEREOF
DE3035149A1 (en) * 1980-09-18 1982-04-22 Bayer Ag, 5090 Leverkusen METHOD FOR THE PRODUCTION OF TRANS-3- (Z-2-CHLORO-2-ARYL-VINYL) -2,2-DIMETHYLCYCLOPROPAN-1-CARBONIC ACID DERIVATIVES, NEW INTERMEDIATE PRODUCTS THEREOF, METHOD FOR THE PRODUCTION THEREOF ADMINISTRATIVE APPLICATION

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0095696A1 (en) * 1982-06-02 1983-12-07 Bayer Ag Process for the preparation of 2,2-dimethyl-3-aryl-cyclopropane carboxylic acids and their esters, intermediate products therefor and processes for their preparation

Also Published As

Publication number Publication date
EP0323625A3 (en) 1990-07-25
US4897505A (en) 1990-01-30
JP2720934B2 (en) 1998-03-04
AU607030B2 (en) 1991-02-21
EP0323625B1 (en) 1992-09-09
DE3800097A1 (en) 1989-07-13
DE3874509D1 (en) 1992-10-15
JPH01203350A (en) 1989-08-16
AU2769889A (en) 1989-07-06
ZA8942B (en) 1989-09-27

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